Electrochemical cell having a safety vent closure and method for assembling same

Description

[0001] This invention relates to a safety, non-resealable vent closure for galvanic cells, e.g. nonaqueous cells, and to a method of producing the safety vent closure of this invention.

[0002] Galvanic cells may generate large quantities of gas under certain conditions during use. Since many such cells are required to be tightly sealed in order to prevent loss of electrolyte by leakage, high internal gas pressures may develop. Such pressures may cause leakage, bulging or possible rupture of the cell's container under abusive conditions if not properly vented.

[0003] In the past, several different types of resealable pressure relief vent valves have been used for releasing high internal gas pressures from inside a sealed galvanic cell. One type of valve that has been commonly used consists basically of a valve member such as a flat rubber gasket which is biased into sealing position over a vent orifice by means of a resilient member such as a helical spring. The resilient member or spring is designed to yield at a certain predetermined internal gas pressure so as to momentarily break the seal and allow the gas to escape through the vent orifice.

[0004] In U.S. Patent No. 3,664,878 to Amthor issued on May 23, 1972, a resealable vent is disclosed which comprises a resilient deformable ball of elastomeric material positioned to overlie a vent orifice provided within the cell's container. A retainer means is positioned over the resilient ball for maintaining the ball in place over the vent orifice and in contact with a valve seat provided around the peripheral edge portions of the vent orifice and for compressing and deforming the resilient ball into a flattened configuration forming a normally fluid-tight seal between the flattened ball and the valve seat. The resilient ball is capable of undergoing further temporary deformation upon the build up of a predetermined high internal gas pressure inside the container so as to momentarily break the seal and allow gas to escape through the vent orifices.

[0005] However, with the continuing development of portable electrically powered devices such as tape recorders and playback machines, radio transmitters and receivers, and the like, a new type of reliable, long service life cells or batteries have been developed. These newly developed electrochemical cell systems provide a long service life by utilizing highly reactive anode materials such as lithium, sodium and the like, in conjunction with high energy density non- aqueous liquid cathode materials and a suitable salt.

[0006] It has recently been disclosed in the literature that certain materials are capable of acting both as an electrolyte carrier, i.e., as solvent for the electrolyte salt, and as the active cathode for a nonaqueous electrochemical cell. U.K. Patent Specification No. 1,409,307 discloses a non- aqueous electrochemical cell comprising an anode, a cathode collector and a cathode-electrolyte, said cathode-electrolyte comprising a solution of an ionically conductive solute dissolved in an active cathode depolarizer wherein said active cathode depolarizer comprises a liquid oxyhalide of an element of Group V or Group VI of the Periodic Table. The "Periodic Table" is the Periodic Table of Elements as set forth on the inside back cover of the Handbook of Chemistry and Physics, 48th Edition, The Chemical Rubber Co., Cleveland, Ohio, 1967-1968. For example, such nonaqueous cathode materials would include sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide and selenium oxychloride.

[0007] Another class of liquid cathode materials would be the halides of an element of Group IV to Group VI of the Periodic Table. For example, such non- aqueous cathode material would include sulfur monochloride, sulfur monobromide, selenium tetrafluoride, selenium monobromide, thiophosphoryl chloride, thiophosphoryl bromide, vanadium pentafluoride, lead tetrachloride, titanium tetrachloride, disulfur decafluoride, tin bromide trichloride, tin dibromide dichloride and tin tribromide chloride.

[0008] It has been found that when employing high energy density liquid cathode materials in non- aqueous cell systems, the cells exhibit higher voltages than cells employing conventional aqueous systems which results in fewer cell units being required to operate a particular battery- powered device. In addition, many of the oxyhalide and halide nonaqueous cells display relatively flat discharge voltage-versus-time curves. Thus these cells can be employed to produce batteries that will provide a working voltage closer to a designated cut-off voltage than is practicable with some conventional aqueous systems which generally do not exhibit flat discharge voltage-versus-time curves.

[0009] However, one possible disadvantage in the use of oxyhalide and halide liquid cathode non- aqueous cells is that it may be possible that during storage or use, some of the oxyhalide, halide or their reaction products may escape from the cell. This escape of liquids and/or gases could cause damage to the device employing the cell or to the surface of a compartment or shelf where the cell is stored. On the other hand, if the seal of the cell is effectively permanently secured, then it is possible that the build up of internal pressure within the cell could cause the cell's container to rupture which may cause property and/or bodily damage. To prevent rupture of the cell's container from possible internal pressure build up caused under abusive conditions, such as charging and exposure to a high temperature environment, it is necessary to vent the cell at some predetermined pressure. It has been reported that some oxyhalides such as thionyl chloride and sulfuryl chloride should be vented at pressures below about 3447.5 x 10³ Pa (about 500 psi) and preferably between about 1034.25 x 10³ and 2068.5 x 10³ Pa (between about 150 and 300 psi).

[0010] Specification DE-B-1,117,771 describes a capacitor overpressure valve comprised of a circular diaphragm disk which is force-fitted within a circular cylindrical flange. Furthermore, the flange surrounds a circular hole in the container of the capacitor.

[0011] Specification GB-A-1,045,855 describes a resealable vent mechanism. That particular vent mechanism comprises a ball-shaped valve body which is urged against a frusto-conical aperture by a coil spring and there is present a layer of oxganosiloxane or fluorinated grease which is disposed over the valve body and within a circular flange which contains the valve mechanism.

[0012] According to the present invention there is provided an electrochemical cell in which the active components of the cell are assembled within a housing comprising a container closed at its open end by a cover and having at least one vent orifice; a safety vent closure comprising a deformable member force-fitted within the vent orifice thereby providing a normally fluid tight seal at said vent orifice; and wherein said deformed member is adapted to be at least partially expelled from the vent orifice upon a build up of a predetermined internal gas pressure inside the cell; characterised by

(i) a conductive tubular member secured to the housing and surrounding the vent orifice and being open at its end remote from the housing,

(ii) a layer of a sealant material disposed within the conductive tubular member over the deformable member and the area of the housing defining the vent orifice surrounded by the conductive tubular member,

the arrangement being such as to provide for the production of a permanent vent on at least partial expulsion of the deformable member.

[0013] The advantage of the sealant material is that it will provide maximum leakage resistance as well as further increased reliability to vent after a predesignated pressure build up. Suitable sealing materials could include wax, halocarbon wax which is a saturated low-molecular weight polymer of chlorotrifluoroethylene having the general formula: -(CH2-CFCl)n-, asphalt, epoxy or any materials which are resistant to moisture, have reasonable adhesion to metal and can be applied easily. Preferably the material should be applied in liquid form and then set to a solid.

[0014] By use of the present invention there may be provided a safety non-resealable vent closure for non-aqueous cells that is inexpensive to manufacture and easy to assemble.

[0015] The invention also relates to a method for assembling an electrochemical cell having a safety vent closure comprising the steps:

a) placing the solid components of a cell within the container of a cell's housing, said housing comprising the container having secured at its open end a cover and said housing having at least one vent orifice;

b) feeding the liquid component of the cell through the vent orifice into the housing; and

c) force-fitting a deformable member into the vent orifice thereby providing a fluid-tight seal over said vent orifice, characterised in that

d) a conductive tubular member is secured to said housing surrounds the vent orifice and is open at its end remote from the housing, and

e) a layer of a sealant is placed within the conductive tubular member over the deformable member and the area of the housing defining the vent orifice surrounded by the conductive tubular member.

[0016] As used herein, the deformable material has to be made of a material or coated with a material that is chemically resistant to the cell's components, particularly the cell's liquid components, and have a hardness greater than 100 on the Shore A scale (as measured on a durometer instrument manufactured by the Shore Instrument Mfg. Co.). The deformable material shall also have modulus of elasticity (Young's Modulus) between about 68.95 x 10⁶ Pa and about 193.06 x 10⁹ Pa and preferably between about 206.85 x 10⁶ Pa and 137.9 x 10⁹ Pa (between about 0.01 x 10⁶ psi and about 28 x 10⁶ psi and preferably between about 0.03 x 10⁶ and 20 x 10⁶ psi). For nonaqueous oxyhalide cell systems, the deformable material can be selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene propylene polymer, perfluoroalkoxyethylene polymer, ethylene tetrafluoroethylene polymer and the like. When the deformable material is to be coated with a chemically inert material, the said deformable material can be selected from the group consisting of nylon, lead, hard rubber and the like. Other suitable material for use in this invention but not suitable for some of the oxyhalide cell systems are nylon, polypropylene, polycarbonate, acrylic polymers and the like.

[0017] As used herein, the tubular member can be cylindrical, square, rectangular or have any polygonal shaped cross section. In the preferred embodiment, the cell will be a cylindrical cell in which the vent orifice is disposed in the cell's cover and wherein the conductive tubular member, which serves as an electrical terminal for the cell, will be a cylindrical member having an outwardly disposed flange at one end which is adapted for securing to the cell's cover. The tubular member is ideally suited as an element to which conductive strips can be welded to serve as external leads. Preferably, the deformable member should have a smooth spherical configuration and the wall defining the vent orifice should be substantially smooth.

[0018] The safety vent closure of this invention can be made to vent at any predetermined pressure build up within the cell by regulating the size of the vent opening with respect to the size of the deformable member, the material of which the deformable member is made, the degree of deformation required of the deformable member upon its insertion into the vent orifice, and the shapes of the vent opening and the deformable member. Using the teachings of this invention, the deformable member could be inserted rapidly into the orifice with a minimum of force to attain a reliable and predictable safety vent closure. The use of a controlled height dead-stop ram to insert the deformable member would be most desirable for automatic assembly operations.

[0019] It has been found that for 1.207 cm (0.475 inch) diameter cells an ideal safety vent closure can be had using a cover thickness of 0.127 cm (0.05 inch), a circular vent orifice of 0.218 cm (0.086 inch) diameter, a deformable ball of polytetrafluoroethylene measuring 0.239 cm (0.094 inch) in diameter and a conventional ram employing a push-in force of 11.34 kg (25 pounds).

[0020] A preferred version of the safety vent closure of this invention utilizes a polytetrafluoroethylene ball with a halocarbon wax overseal in which the ball is comprssed 10 to 15 per cent upon insertion into a vent opening in a lithium/oxyhalide cell. Once inserted, the ball will assume a substantially spherical configuration. Cells of this type were tested and found to exhibit no leakage at 25°C and 100% relative humidity over long periods of time. In the abuse testing of these type cells wherein the cells were charged at up to 2 amperes and on testing of the cells in an incinerator at temperatures as high as 865°C, all the cells vented properly without any container rupture. Thus the subject invention is ideally suited for lithium/oxyhalide cell systems, specifically those employing sulfuryl chloride and/or thionyl chloride.

[0021] The safety non-resealable vent closure of this invention preferably can be employed with all size cylindrical cells and is ideally suited for liquid cathode cell systems employing, for example, a liquid oxyhalide. In addition to providing an excellent and effective safety venting means, the invention also permits the initial assembling of the solid components of a cell within a container that can be closed in a conventional manner before adding the cell's liquid component. When the cell's liquid component is an oxyhalide-based liquid cathode, such as thionyl chloride or sulfuryl chloride, then these corrosive liquids can be injected into the cell's housing through the small vent orifice, e.g., by vacuum filling, after the cell cover is secured to the container. This will effectively eliminate the corrosion of crimping equipment used to close the cell as well as eliminating contamination at the interfaces of the container- gasket and gasket-cover of the cell by the oxyhalide.

[0022] A cell for use in this invention can be the split internal anode/outer cathode collector construction as described in U.S. Patent 4,032,696 or the split internal cathode collector construction as described in U.S. Patent 4,048,389, said U.S. Patents 4,032,696 and 4,048,389 being incorporated herein by reference.

[0023] Suitable nonaqueous liquid cathode materials for use in cells of this invention could be one or more of the liquid oxyhalides of an element of Group V or Group VI of the Periodic Table and/or one or more of the halides of an element of Group IV to Group VI of the Periodic Table, said Periodic Table being the Periodic Table of Elements as set forth on the inside back cover of the Handbook of Chemistry and Physics, 48th Edition, The Chemical Rubber Co., Cleveland, Ohio, 1967-1968. For example, such nonaqueous cathode materials would include sulfuryl chloride, thionyl chloride, phosphorus oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide, selenium oxychloride, sulfur monochloride, sulfur monobromide, selenium tetrafluoride, selenium monobromide, thiophosphoryl chloride, thiophosphoryl bromide, vanadium pentafluoride, lead tetrachloride, titanium tetrachloride, disulfur decafluoride, tin bromide trichloride, tin dibromide dichloride and tin tribromide chloride. Another suitable cathode material would be liquid sulfur dioxide.

[0024] Anodes suitable for use in nonaqueous liquid cathode cell systems can be generally consumable metals and include the alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and other metals. The term "alloy" as used herein is intended to include mixtures; solid solutions such as lithium- magnesium; and intermetallic compounds such as lithium monoaluminide. The preferred anode materials are the alkali metals and particularly lithium, sodium and potassium. When using lithium anodes the anode may be coated with a vinyl resin as disclosed in U.S Patent 3,993,501, said patent incorporated herein by reference.

[0025] The cathode collector for use in liquid cathode cell systems has to be electronically conductive so as to permit external electrical contact to be made with the active cathode material and also provide extended area reaction sites for the cathodic electrochemical process of the cell. Materials suitable for use as a cathode collector are carbon materials and metal such as nickel, with acetylene black being preferable. In addition, the cathode collector when made of a particulate material should be capable of being moulded directly within a can or capable of being moulded into various size discrete bodies that can be handled without cracking or breaking. To impart a cohesive characteristic to some types of cathode collectors, such as carbonaceous cathode collectors, a suitable binder material, with or without plasticizers and with or without stabilizers, can be added to the cathode collector materials. Suitable binder materials for this purpose may include vinyl polymers, polyethylene, polypropylene, polyacrylics, polystyrene and the like. For example, polytetrafluoroethylene would be the preferred binder for cathode collectors for use with liquid oxyhalide cathodes. The binder, if required, should be added in an amount between about 5% and about 30% by weight of the moulded cathode collector since an amount less than 5% would not provide sufficient strength to the moulded body while an amount larger than 30% would wetproof the surface of the carbon and/or reduce the available surface of the carbon, thereby reducing the activation site areas required for the cathodic electrochemical process of the cell. Preferably, the binder should be between 10% and 25% by weight of the cathode collector. Of importance in selecting the materials for the cathode collector is to select materials that will be chemically stable in the cell system in which they are to be used.

[0026] A solute for use in liquid cathode cell systems may be a simple or double salt which will produce an ionically conductive solution when dissolved in a suitable solvent. Preferred solutes for non- aqueous systems are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The only requirements for utility are that the salt, whether simple or complex, be compatible with the solvent being employed and that it yield a solution which is ionically conductive. According to the Lewis or electronic concept of acids and bases, many substances which contain no active hydrogen can act as acids or acceptors of electron doublets. The basic concept is set forth in the chemical literature (Journal of the Franklin Institute, Vol. 226, July/December, 1938, Pages 293-313 by G. N. Lewis).

[0027] A suggested reaction mechanism for the manner in which these complexes function in a solvent is described in detail in U.S. Patent 3,542,602 wherein it is suggested that the complex or double salt formed between the Lewis acid and the ionizable salt yields an entity which is more stable than either of the components alone.

[0028] Typical Lewis acids suitable for use in conjunction with liquid oxyhalide cathodes include aluminium fluoride, aluminium bromide, aluminium chloride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, boron fluoride, boron chloride and boron bromide.

[0029] Ionizable salts useful in combination with the Lewis acids include lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, potassium fluoride, potassium chloride and potassium bromide.

[0030] It will be obvious to those skilled in the art that the double salts formed by a Lewis acid and an ionizable salt may be used as such or the individual components may be added to the solvent separately to form the salt or the resulting ions in situ. One such double salt, for example, is that formed by the combination of aluminium chloride and lithium chloride to yield lithium aluminium tetrachloride.

[0031] If desired, and specifically for the halides, a cosolvent should be added to the liquid active reducible cathode and solute solution to alter the dielectric constant, viscosity or solvent properties of the solution to achieve better conductivity. Some examples of suitable cosolvents are nitrobenzene, tetrahydrofuran, 1,3-dioxolane, 3-methyl-2-oxazolidone, propylene carbonate, y-butyrolactone, sulfolane, ethylene glycol sulfite, dimethyl sulfite, benzoyl chloride, dimethoxyethane, dimethyl isoxazole, diethyl carbonate, sulfur dioxide and the like.

[0032] Suitable separators for use with liquid cathodes in nonaqueous cells suitable for use in non- aqueous liquid cathode cell systems are the nonwoven glass separators, preferably those separators that incorporate long glass fibers along with the short glass fibers since such a combination increases the tear strength of the separators thereby making them easier to handle.

[0033] The container of the cell could be made of stainless steel, iron, nickel, plastic, coated metals or some other suitable material.

[0034] Some preferred combinations of nonaqueous cathode materials and anodes would be as follows:

1) sulfuryl chloride/Li or Na;

2) thionyl chloride/Li or Na;

3) phosphorus oxychloride/Li or Na;

4) sulfur monochloride/Li or Na;

5) sulfur monobromide/Li or Na;

6) selenium tetrafluoride/Li or Na.

[0035] Preferably, the cells for use in this invention would be liquid oxyhalide cells using sulfuryl chloride, thionyl chloride or mixtures thereof with a lithium anode.

[0036] It is to be understood that the safety vent closure of this invention could be used in other cell systems such as, for example, Leclanche dry cells, zinc chloride cells, lithium-Mn0₂ cells, lithium-iron sulfide cells, alkaline-Mn0₂ cells, nickel-cadmium cells, and lead-acid cells.

[0037] The present invention will become more apparent from the following description thereof when considered together with the accompanying drawing which is set forth as being exemplary of embodiments of the present invention and is not intended in any way to be limitative thereof and wherein

Figure 1 is a vertical cross sectional view of an electrochemical cell having its solid components fully assembled within a housing and being ready for receiving the liquid component of the cell.

Figure 2 is an enlarged horizontal cross sectional view taken along line 2-2 of Figure 1.

Figure 3 is a partial vertical cross sectional view of the cell of Figure 1 after the addition of the liquid component and just prior to inserting the deformable ball into the orifice in the cell's cover.

Figure 4 is a partial vertical cross sectional view of the cell of Figure 3 after the deformable ball is forced fitted into the vent orifice in the cell's cover.

Figure 5 is a partial vertical cross sectional view of a fully assembled cell.

[0038] Referring in detail to Figure 1, there is shown a cross sectional view of a cylindrical cell comprising a cylindrical container 2 having disposed therein a cathode collector shell 4 in contact with the inner upstanding circumference of the container 2 thereby adapting the container as the cathodic or positive terminal for the cell. Disposed within and in contact with the inner circumference of cathode collector 4 is a separator liner 6 with its bottom separator or disc 10. If desired, the cathode collector material could be extruded within the container 2, rolled with the container material or composed of one or more segments to form a cylindrical tube and then placed in the can.

[0039] A two member anode 12 is shown in Figures 1 and 2 comprising a first half cylindrical annular member 14 having flat end faces 16 and 18 and a second half cylindrical annular member 20 having flat end faces 22 and 24. When the flat end faces of each cylindrical half member are arranged in an opposing fashion as shown in Figures 1 and 2, an axial cavity 26 is defined between the cylindrical half annular members 14 and 20.

[0040] If desired, arcuate type backing sheets 15 and 17, such as inert electrically conductive metal screens or grids, could be disposed against the inner surface wall of the anode bodies 14 and 20, respectively, to provide uniform current distribution over the anode. This will result in a substantially uniform consumption or utilization of the anode while also providing a substantially uniform spring pressure over the inner wall surface of anode as will be discussed below.

[0041] An electrically conductive spring strip 28 is appropriately bent into a flattened elliptically shaped member having an extending end 30. When inserting the spring strip 28 into a container, the legs 32, 34 of the conductive strip 28 are squeezed together and forced into the axial opening between the two screen backed anode members arranged in a container as shown in Figures 1 and 2. The inserted conductive spring strip 28 resiliently biases the two anode members 14 and 20 via backing screens 15 and 17 so as to provide a substantially uniform and continuous pressure contact over the inner wall of the anode members. The extended end 30 of spring strip 28 is shown projected above the surface of anode members 14 and 10. An insulating gasket 36 has a central opening 38 through which the projected end 30 of the spring strip 28 passes, whereupon the end 30 is then welded to a cover 40 thereby adapting the cover 40 as the anodic or negative terminal of the cell.

[0042] Secured to the cover 40 is a cylindrical cap 42. Specifically, the cylindrical cap comprises a conductive cylindrical segment 41 terminating at one end with an outwardly oriented flange 44 which is secured to cover 40.

[0043] The insulating gasket 36 has a peripheral depending skirt 52 disposed between the cover 40 and the upper inner wall of the container 2 for closing the cell through conventional crimping techniques. As shown in Figure 1, the cylindrical cap is secured to the cover 40 and the cell is closed using conventional crimping techniques with all of the solid components of the cell assembled within the container 2. After the cell is assembled with the solid components, a hypodermic needle 54 or the like is used to inject the liquid component into the assembled cell. Specifically, a cathode-electrolyte comprising a suitable salt dissolved in an oxyhalide, a halide with a cosolvent or mixtures thereof can be dispensed through the cover vent orifice 25 into cavity 26 using the hypodermic needle 54 whereupon it can penetrate through the separator and cathode collector of the cell.

[0044] As shown in Figure 3, with the cell's liquid component fed into the container, a polytetrafluoroethylene deformable ball 56 is disposed over opening 25 in cover 40 and then a ram member 58 is used to force ball 56 into vent orifice 25 as shown in Figure 4. After removal of the ram 58, a layer of a sealant 60 is disposed over ball 56 and cover 40 within cylindrical member 42 producing a fully sealed cell employing the safety vent closure of this invention.

[0045] Preferably prior to the adding of the liquid component of the cell, a vacuum could be created within the cell whereupon the liquid component could then be drawn effectively into the cell and uniformly distributed therein.

[0046] The safety vent closure of this invention will provide a means for venting a rapidly generated high pressure gas built up within a cell thereby preventing the rupture of the cell's container.

[0047] The following examples are illustrative of the present invention and are not intended in any manner to be limitative thereof.

Example 1

[0048] Several cells were made in accordance with Figures 1 to 5 using the following components: anode of lithium,

[0049] cathode collector of polytetrafluoroethylene- bonded acetylene black, and

[0050] thionyl chloride containing 1.5M LiAICI₄.

[0051] Each cell measured 1.207 cm (0.475 inch) diameter and was 4.14 cm (1.63 inches) long. The vent orifice measured 0.277 cm (0.109 inch) in diameter and was 0.127 cm (0.05 inch) long. The polytetrafluoroethylene ball was 0.318 cm (0.125 inch) in diameter and was force-fitted into the vent orifice as shown in Figure 4. A layer of halocarbon wax (obtained from Halocarbon Industries, New Jersey) was deposited over the polytetrafluoroethylene ball and the area defining vent orifice as shown in Figure 5.

[0052] Several of the above-described cells were heated in a direct flame at a temperature up to about 865°C. All of the cells vented without rupturing the cells' containers. Contrary to this, cells using the above-identified components and sealed in a conventional manner would generally show some container rupture when subjected to the same test conditions.

Example 2

[0053] Several cells were constructed using the same components as in Example 1 and employing the resealable vent closure of this invention. The cells were charged at 2 amperes and all were observed to vent without rupturing of the cells' containers. Contrary to this, cells using the above-identified components and sealed in a conventional manner would generally show some container rupture when subjected to the same test conditions.

Claims

1. An electrochemical cell in which the active components of the cell are assembled within a housing comprising a container (2) closed at its open end by a cover (40) and having at least one vent orifice (25); a safety vent closure comprising a deformable member (56) force-fitted within the vent orifice (25) thereby providing a normally fluid tightseal at said vent orifice; and wherein said deformed member is adapted to be at least partially expelled from the vent orifice upon a build up of a predetermined internal gas pressure inside the cell; characterised by

(i) a conductive tubular member (41) secured to the housing and surrounding the vent orifice (25) and being open at its end remote from the housing,

(ii) a layer of a sealant material (60) disposed within the conductive tubular member (41) over the deformable member (56) and the area of the housing defining the vent orifice (25) surrounded by the conductive tubular member (41),

the arrangement being such as to provide for the production of a permanent vent on at least partial expulsion of the deformable member.

2. An electrochemical cell as claimed in claim 1, characterised in that the sealant material (60) is selected from asphalt, wax, halocarbon wax and epoxy.

3. An electrochemical cell as claimed in claim 1 or 2, characterised in that the vent orifice (25) is disposed in the cover (40) and the conductive tubular member (41) is a cylindrical member.

4. An electrochemical cell as claimed in any one of the preceding claims, characterised in that the deformable member (56) has a hardness greater than 100 Durometer and a Modulus of Elasticity between about 68.95 x 10⁶ Pa and about 193.06 x 10⁹ Pa (between about 0.01 x 10⁶ psi and about 28 x 10⁶ psi).

5. An electrochemical cell as claimed in any one of the preceding claims, characterised in that the deformable material is selected from polytetrafluoroethylene, fluorinated ethylene propylene polymer, perfluoroalkoxyethylene polymer, ethylene tetrafluoroethylene polymer, nylon, polypropylene, polycarbonate and acrylic polymers.

6. An electrochemical cell as claimed in any one of the preceding claims, characterised in that the deformable material is coated with a chemically inert material with respect to the components of the cell.

7. An electrochemical cell as claimed in any one of the preceding claims, characterised in that the deformable member (56) has a substantially spherical configuration.

8. An electrochemical cell as claimed in any one of the preceding claims, characterised in that it employs a cathode-electrolyte which contains at least one liquid oxyhalide selected from thionyl chloride, sulfuryl chloride, phosphorous oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide and selenium oxychloride.

9. An electrochemical cell as claimed in claim 8, characterised in that the at least one liquid oxyhalide is selected from thionyl chloride and sulfuryl chloride.

10. An electrochemical cell as claimed in any one of the preceding claims, characterised in that it employs an anode selected for lithium, sodium calcium, potassium and aluminium.

11. A method for assembling an electrochemical cell having a safety vent closure (25) comprising the steps:

a) placing the solid components of a cell within the container (2) of a housing of the cell, said housing comprising the container having secured at its open end a cover (40) and said housing having at least one vent orifice (25);

b) feeding the liquid component of the cell through the vent orifice (25) into the housing; and

c) force-fitting a deformable member (56) into the vent orifice (25) thereby providing a fluid-tight seal over said vent orifice, characterised in that

d) a conductive tubular member is secured to said housing surrounds the vent orifice (25) and is open at its end remote from the housing, and

e) a layer of a sealant (60) is placed within the conductive tubular member (41) over the deformable member (56) and the area of the housing defining the vent orifice (25) surrounded by the conductive tubular member (41).

12. A method as claimed in claim 11, characterised in that the liquid component of the electrochemical cell in step b) is a cathode-electrolyte which comprises at least one liquid oxyhalide selected from thionyl chloride, sulfuryl chloride phosphorous oxychloride, thionyl bromide, chromyl chloride, vanadyl tribromide and selenium oxychloride.

13. A method as claimed in claim 11 or 12, characterised in that the electrochemical cell employs a solid anode selected from lithium, sodium, calcium, potassium and aluminium.

Ansprüche

1. Elektrochemische Zelle, bei der die aktiven Bestandteile der Zelle innerhalb eines Gehäuses angeordnet sind mit einem Behälter (2), der an seinem offenen Ende mittels einer Abdeckung (40) verschlossen ist und mindestens eine Entgasungsöffnung (25) aufweist, mit einem Sicherheitsventilverschluß, der ein in die Entgasungsöffnung (25) eingedrücktes verformbares Teil (56) beinhaltet und hierdurch ein normalerweise fluiddichter Verschluß der Entgasungsöffnung geschaffen ist, und wobei das verformbare Teil dazu vorgesehen ist, zumindest teilweise aus der Entgasungsöffnung gestoßen zu werden, sobald sich ein vorherbestimmter Gasdruck innerhalb der Zelle aufgebaut hat, gekennzeichnet durch

(i) ein leitendes röhrenförmiges Teil (41), das am Gehäuse befestigt ist und die Entgasungsöffnung (25) umgibt und an dessen gegenüber dem Gehäuse entfernten Ende offen ist,

(ii) eine Dichtungsmaterialschicht (60), die innerhalb des leitenden röhrenförmigen Teils (41) über dem verformbaren Teil (56) und dem die Entgasungsöffnung (25) bildenden Bereich des Gehäuses, der vom leitenden röhrenförmigen teil (41) umgeben ist, angeordnet ist,

wobei die Anordnung derart ist, daß eine dauerhafte Entgasung bei einem zumindest teilweisen Ausstoß des verformbaren Teils erfolgt.

2. Elektrochemische Zelle nach Anspruch 1, dadurch gekennzeichnet, daß das Dichtungsmaterial (60) aus Asphalt, Wachs, Halocarbonwachs und Epoxy besteht.

3. Elektrochemische Zelle nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Entgasungsöffnung (25) in der Abdeckung (40) angeordnet ist und das leitende Teil (41) ein zylindrisches Teil ist.

4. Elektrochemische Zelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das verformbare Teil (56) eine Härte größer als 100 Durometer und einen Elastizitätsmodul zwischen etwa 68,95 x 10⁶ Pa und etwa 193,06 x 10⁹ Pa (zwischen etwa 0,01 x 10⁶ psi und etwa 28 x 10⁶ psi) aufweist.

5. Elektrochemische Zelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das verformbare Material aus Polytetrafluoräthylen, fluoriertem Äthylen-Propylen-Polymer, Perfluoralkoxyäthylen-Polymer, Äthylen-Tetrafluoräthylen-Polymer, Nylon, Polypropylen, Polycarbonat und Acrylpolymeren besteht.

6. Elektrochemische Zelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das verformbare Material mit einem bezüglich der Komponenten der Zelle chemisch inerten Material überzogen ist.

7. Elektrochemische Zelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das verformbare Teil (56) eine im wesentlichen kugelförmige Gestalt aufweist.

8. Elektrochemische Zelle nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie einen Kathodenelektrolyt verwendet, der wenigstens ein flüssiges Oxihalogenid aus der Gruppe des Thionylchlorids, des Sulfurylchlorids, des Phosphoroxichlorids, des Thionylbromids, des Chromylchlorids, des Vanadyltribromids und des Selenoxichlorids enthält.

9. Elektrochemische Zelle nach Anspruch 8, dadurch gekennzeichnet, daß wenigstens ein flüssiges Oxihalogenid aus der Gruppe des Thionylchlorids und des Sulfurylchlorids ausgewählt ist.

10. Elektrochemische Zelle nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß sie eine Anode aus der Gruppe Lithium, Natrium, Calcium, Kalium und Aluminium aufweist.

11. Verfahren zur Herstellung einer elektrochemischen Zelle mit einem Sicherheitsventilverschluß (25) mit den Verfahrenschritten:

a) Anordnen der festen Bestandteile einer Zelle innerhalb des Behälters (2) eines Zellengehäuses, zu welchem dieser Behälter gehört, an dessen offenem Ende eine Abdeckung (40) befestigt ist und welches wenigstens eine Entgasungsöffnung (25) aufweist;

b) Einfüllen des flüssigen Bestandteils der Zelle durch die Entgasungsöffnung (25) in das Gehäuse; und

c) Eindrücken eines verformbaren Teils (56) in die Entgasungsöffnung (25), wodurch ein fluiddichter Verschluß über der Entgasungsöffnung geschaffen wird, dadurch gekennzeichnet, daß

d) ein leitendes röhrenförmiges Teil an dem Gehäuse die Entgasungsöffnung (25) umgebend befestigt ist und an dessen dem Gehäuse entfernten Ende offen ist, und

e) eine Dichtschicht (60) innerhalb des leitenden röhrenförmigen Teils (41) über dem verformbaren Teil (56) und dem Bereich des Gehäuses, der die Entgasungsöffnung (25) bildet und von dem leitenden röhrenförmigen Teil (41) umgeben ist, angeordnet ist.

12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß der flüssige Bestandteil der elektrochemischen Zelle in Schritt (b) ein Kathodenelektrolyt ist, der wenigstens eine flüssiges Oxihalogenid aus der Gruppe Thionylchlorid, Sulfurylchlorid, Phosphoroxichlorid, Thionylbromid, Chromylchlorid, Vanadyltribromid und Selenoxichlorid aufweist.

13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß für die elektrochemische Zelle eine feste Anode aus der Gruppe Lithium, Natrium, Calcium, Kalium und Aluminium verwendet wird.

Revendications

1. Pile électrochimique dans laquelle les constituants actifs de la pile sont assemblés à l'intérieur d'un boîtier comprenant un récipient (2) fermé à son extrémité ouverte par un couvercle (40) et présentant au moins un orifice d'évent (25); une fermeture à évent de sûreté comprenant un élément déformable (56) emmanché à force dans l'orifice d'évent (25) afin de former un joint normalement étanche aux fluides audit orifice d'évent; et dans laquelle ledit élément déformé est conçu pour être au moins partiellement expulsé de l'orifice d'évent à la suite d'une accumulation d'une pression gazeuse interne prédéterminée à l'intérieur de la pile; caractérisée par

(i) un élément tubulaire conducteur (41) fixé au boîtier et entourant l'orifice d'évent (25) et ouvert à son extrémité éloignée du boîtier,

(ii) une couche de matière (60) d'obturation étanche disposée à l'intérieur de l'élément tubulaire conducteur (41) au-dessus de l'élément déformable (56) et de la zone du boîtier définissant l'orifice d'évent (25) entourée de l'élément tubulaire conducteur (41),

l'agencement étant tel qu'il assure l'établissement d'un évent permanent lors d'une expulsion au moins partielle de l'élément déformable.

2. Pile électrochemique selon la revendication 1, caractérisée en ce que la matière (60) d'obturation étanche est choisie parmi de l'asphalte, de la cire, de la cire halogénocarbonée et un époxy.

3. Pile électrochimique selon la revendication 1 ou 2, caractérisée en ce que l'orifice d'évent (25) est disposé sur le couvercle (40) et l'élément tubulaire conducteur (41) est un élément cylindrique.

4. Pile électrochimique selon l'une quelconque des revendications précédentes, caractérisée en ce que l'élément déformable (56) présente une dureté supérieure à 100 au duromètre et un module d'élasticité compris entre environ 68,95 x 10⁶ Pa et environ 193,06 x 10⁹ Pa (entre environ 0,01 x 10⁶ psi et environ 28 x 10⁶ psi).

5. Pile électrochimique selon l'une quelconque des revendications précédentes, caractérisée en ce que la matière déformable est choisie parmi le polytétrafluoréthylène, un polymère propylène- éthylène fluoré un polymère de perfluoralkoxy- éthylène, un polymère éthylène-tétrafluor- éthylène, du Nylon, un polypropylène, un polycarbonate et des polymères acryliques.

6. Pile électrochimique selon l'une quelconque des revendications précédentes, caractérisée en ce que la matière déformable est revêtue d'une matière chimiquement inerte vis-à-vis des constituants de la pile.

7. Pile électrochimique selon l'une quelconque des revendications précédentes, caractérisée en ce que l'élément déformable (56) présente une configuration sensiblement sphérique.

8. Pile électrochimique selon l'une quelconque que des revendications précédentes, caractérisée en ce qu'elle utilise un électrolyte-cathode qui contient au moins un oxyhalogénure liquide choisi parmi le chlorure de thionyle, le chlorure de sulfuryle, l'oxychlorure de phosphore, le bromure de thionyle, le chlorure de chromyle, le tribromure de vanadyle et l'oxychlorure de sélénium.

9. Pile électrochimique selon la revendication 8, caractérisée en ce que l'oxyhalogénure liquide est choisi entre le chlorure de thionyle et le chlorure de sulfuryle.

10. Pile électrochimique selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle utilise un anode choisie parmi le lithium, le sodium, le calcium, le potassium et l'aluminium.

11. Procédé d'assemblage d'une pile électrochimique comportant une fermeture (25) à évent de sûreté comprenant les étapes qui consistent:

a) à placer les constituants solides d'une pile à l'intérieur du récipient (2) d'un boîtier de la pile, ledit boîtier comprenant le récipient à l'extrémité ouverte duquel est fixé un couvercle (40) et ledit boîtier présentant au moins un orifice d'évent (25);

b) à introduire le constituant liquide de la pile dans le boîtier par l'intermédiaire de l'orifice d'évent (25); et

c) à emboîtier à force un élément déformable (56) dans l'orifice d'évent (25) afin d'établir un joint étanche aux fluides sur ledit orifice d'évent, caractérisé en ce que

d) un élément tubulaire conducteur est fixé audit boîtier autour de l'orifice d'évent (25) et est ouvert à son extrémité éloignée du boîtier, et

e) une couche de matière (60) d'obturation étanche est placée à l'intérieur de l'élément tubulaire conducteur (41) au-dessus de l'élément déformable (56) et de la zone du boîtier définissant l'orifice d'évent (25) entourée par l'élément tubulaire conducteur (41).

12. Procédé selon la revendication 11, caractérisé en ce que le constituant liquide de la pile électrochimique de l'étape b) est un électrolyte-cathode qui comprend au moins un oxyhalogénure liquide choisi parmi le chlorure de thionyle, le chlorure de sulfuryle, l'oxychlorure de phosphore, le bromure de thionyle, le chlorure de chromyle, le tribromure de vanadyle et l'oxychlorure de sélénium.

13. Procédé selon la revendication 11 ou 12, caractérisé en ce que la pile électrochimique utilise une anode solide choisie parmi le lithium, le sodium, le calcium, le potassium et l'aluminium.

Drawing